JP2002278129A - Toner and method for image formation, and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide toner for image formation which can suppress fading and the formation of a development stripe and reduce cartridge shaking performed when toner nearly runs short. SOLUTION: At least the toner T for developing an electrostatic charge image, a developer container 12a which contains the toner, and a developer carrier 4 for carrying the toner put in the developer container are included as a developing means; and the developer container has an oblique surface for moving the stored toner from in the developer storage container to the developer carrier side and the angle θ of the oblique surface to the horizontal surface is 20 to 80 deg.. The developer carrier has an outer peripheral diameter of <=15 mm and rotates at a surface peripheral speed of >=65 mm/second and the toner satisfies 1.0<=ψ/ϕ<=2.8, where ψ is the angle of contact with water and ϕ is the angle of the contact of the oblique surface with the water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming toner used for electrophotography, electrostatic recording, electrostatic printing, toner jet, and the like, an image forming method, and a process cartridge.

[0002]

2. Description of the Related Art In recent years, the number of Internet users has rapidly increased due to the innovation of IT technology, and the number of printers operating on a network, printers used in SOHO, and printers used by individuals has increased dramatically. Applications of image forming apparatuses such as electrophotographic printers have also been widespread, and there is a demand for an apparatus configuration that catches up with user needs. For example, there is a demand for an apparatus configuration that reduces the maintenance load on a space-saving machine due to downsizing of component parts, a printer for notifying that the toner has run out, a cartridge that can be used until the toner runs out without shaking the cartridge, and the like. Also, in combination with an image input device such as a scanner,
As the number of opportunities for performing simple copying increases, a printer as an output device is required to have not only faithful reproducibility of fine characters and fine lines but also high-quality graphics output.

Conventionally, as an electrophotographic printer, an electric latent image is formed on a photoreceptor by various means using a photoconductive substance, and the latent image is developed using toner.
Then, after transferring the toner image to the transfer material, heating, pressing,
Fixing is performed by heating and pressurizing or solvent vapor to obtain a copy. The toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above steps are repeated.

As a developing system, there are a one-component developing system and a two-component developing system. Among them, many of them are excellent in suggesting a one-component developing system using magnetic toner particles. For example, Japanese Patent Application Laid-Open No. 54-43036 discloses that a magnetic toner is used as a one-component developer, the toner is applied very thinly on a developing sleeve as a developer carrier, and this is frictionally charged. A method has been proposed in which the toner is developed under the action of a magnetic field of a magnet incorporated in the developing sleeve, in a very close proximity to the latent image on the image carrier without being brought into contact with the latent image, thereby developing the latent image.

In this method, the toner is applied very thinly on the developing sleeve, so that the chance of contact between the developing sleeve and the toner is increased and sufficient frictional charging of the toner is enabled; The toner and the toner are sufficiently rubbed with each other while the toner particles are sufficiently coagulated by moving the magnet and the toner relatively to each other; An excellent image can be obtained by preventing development of the background fog by developing the toner image so as not to contact the latent image.

To increase the number of prints per unit time, it is necessary to increase the speed in the circumferential direction of the developing sleeve. However, the image quality obtained by the configuration of the developing device varies. For example, in the case of small machines required for personal use, in order to survive market competition, miniaturization of component parts,
Inevitably, the number of components has been reduced, and the diameter of the developing sleeve has been reduced, and the developer stirring configuration has been reviewed. As a result, when a small-diameter developing sleeve is used in a developing device having a simple stirring mechanism, increasing the circumferential speed causes insufficient toner supply to the developing sleeve and insufficient triboelectric charging of the toner due to circulation in the developing container. As a result, the halftone image quality may be impaired, or the number of times of cartridge swing may increase.

Conventionally, a developer accommodating container is provided with a rotatable toner agitating member for agitating / supplying toner inside a container molded of a general-purpose resin. Therefore, the shape of the developer accommodating container is limited to a substantially cylindrical shape, and the freedom in design such as a flat shape or a square shape is limited. In order to solve the above-mentioned problems, many studies have been made on the device, such as adding an auxiliary member and improving the configuration of a developing device. However, these solutions increase the cost of the main body and are not preferable in providing a personal printer, and there is still room for improvement.

In order to solve the above problems, some studies have been made on toner itself.

For example, Japanese Patent Application Laid-Open No. 06-313985 attempts to improve the image quality by specifying the physical properties of the surface depth of the developer carrier and the physical properties of the binder resin contained in the toner. Japanese Patent Application Laid-Open No. H11-282201 attempts to improve image quality by defining physical properties of wax and magnetic particles contained in a toner.

In any of the studies, attention is focused on the physical properties of the toner constituent materials, and not on the physical properties of the developer container and the toner itself. Therefore, in a small-sized process cartridge, the toner adheres to the developer container, and the number of run-out toners may be shortened, and the number of times of cartridge swing may increase.

As described above, the image forming toner including the toner, the image forming method, and the process cartridge are still insufficient, and at present, there are some points to be improved.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming toner, an image forming method and a process cartridge which solve the above-mentioned problems.

An object of the present invention is to provide an image forming toner, an image forming method and a process cartridge which suppress the occurrence of fading.

It is a further object of the present invention to provide an image forming toner, an image forming method, and a process cartridge, which reduce the number of times the cartridge is shaken immediately before the toner runs out.

It is a further object of the present invention to provide an image forming toner, an image forming method, and a process cartridge which suppress the occurrence of development streaks.

[0016]

According to the present invention, there is provided an image forming method comprising at least a step of developing an electrostatic image by a developing means having a toner to form a toner image on an electrostatic image carrier. As at least, a toner for developing an electrostatic image, a developer accommodating container for accommodating the toner, and at least a developer carrier for carrying and transporting the toner accommodated in the developing container, The developer storage container has a slope for transferring the stored toner from the inside of the developer storage container to the developer carrier, and the angle θ of the slope with respect to the horizontal plane satisfies the following condition: 20 ° ≦ θ ≦ 80 ° A developing device that satisfies the conditions is used, the developer carrier has an outer peripheral diameter of 15 mm or less, and a peripheral speed of 65
1. An image forming toner for use in an image forming method which rotates at a speed of at least mm / sec. ≦ ψ / φ ≦ 2.8.

According to the present invention, there is provided an image forming method comprising at least a step of developing an electrostatic image by a developing means having a toner to form a toner image on an electrostatic image carrier.
A toner for developing an electrostatic image,
At least a developer accommodating container for accommodating the toner and a developer carrier for carrying and transporting the toner accommodated in the developing container, wherein the developer accommodating container contains the contained toner. A developing device having an inclined surface for shifting from the inside of the developer storage container to the developer carrier is used,
The developer carrier has an outer diameter of 15 mm or less, and rotates at a circumferential speed of 65 mm / sec or more on the surface. The angle θ of the slope with respect to the horizontal plane, and the contact angle φ of the slope with water, A contact angle 方法 of the toner with water satisfies the following condition: 20 ° ≦ θ ≦ 80 ° 1.0 ≦ ψ / φ ≦ 2.8.

Further, the present invention relates to a process cartridge detachably mounted on the main body of an image forming apparatus, wherein the process cartridge has an electrostatic image carrier for holding an electrostatic image and develops the electrostatic image. At least a developing device having a toner for developing the toner, the developing device includes a toner for developing an electrostatic charge image, a developer accommodating container for accommodating the toner, and a developer accommodating container. At least a developer carrier for carrying and transporting the toner, the developer carrier having an outer diameter of 15 mm.
mm, and the peripheral speed of the surface rotates at 65 mm / sec. The developer storage container has an inclined surface for transferring the stored toner from the developer storage container to the developer carrier side. The angle θ of the slope with respect to the horizontal plane, the contact angle φ of the slope with water, and the contact angle 該 of the toner with water satisfy the following conditions: 20 ° ≦ θ ≦ 80 ° 1.0 ≦ ψ / A process cartridge satisfying φ ≦ 2.8.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventor considers the reason why the image forming toner and the image forming method according to the present invention exhibit an original effect as follows.

In a developing device used in a personal small printer, the diameter of the developer carrier tends to be reduced.
In this developing device, it is necessary to rotate the developer carrier with respect to the latent image carrier in order to compensate for a reduction in the development nip between the developer carrier and the latent image carrier. However,
In printer downsizing, the output of the drive system motor is also limited, so that a single motor often also drives the paper transport device, the fixing device, and the developing device, and the drive assigned to the developer carrier and the toner stirring device. Torque is limited.

Under these circumstances, in order to increase the speed and improve the usability with a small printer, the toner supply to the toner carrier is increased even if the circumferential speed of the developer carrier having a small outer diameter is increased. A toner circulation mechanism without a shortage of the amount becomes important. In particular, in systems where the torque allocated to toner agitation is low, or where the cost of toner circulation is not expected to increase, instead of these improvements, control the interaction between the toner and the shape of the developing container or the surface of the container where the toner contacts. It is essential to do.

Therefore, as a result of intensive studies, the outer peripheral diameter of the developer carrying member is 15 mm or less, and the peripheral speed of the developer carrying surface is 65 mm / sec or more (preferably 65 to 260 mm / sec).
Sec), the slope angle θ of the developer container, the contact angle 水 of the developer container slope with water, and the contact angle φ of the toner with water.
It has been found that the above problem can be solved by controlling.

That is, as shown in FIG.
The slope angle θ of the container surface facing the developer carrier 4 is 20
When the angle is set in the range of 80 ° to 80 °, toner circulation is performed smoothly, fading is suppressed, and the number of times of cartridge swinging is reduced. If the angle is smaller than 20 °, it is difficult for the toner to slide on the slope due to its own weight, causing a problem in supplying the toner to the developer carrying member and causing fading. If the angle is larger than 80 °, the volume of the developing container is significantly reduced, so that the desired number of sheets cannot be printed with a small machine.

Further, by setting the ratio of Δ / φ to 1.0 to 2.8, the interaction between the toner and the surface of the developing container can be controlled. If the ratio of Ψ / φ is smaller than 1, that is, if the slope of the developing container is more hydrophobic than the toner, the frictional charge generated when the toner stirring member comes into contact with the surface of the developing container is increased, and the development is caused by electrostatic interaction. As the amount of toner attached to the container increases, even if the cartridge is shaken,
It becomes difficult to print out a predetermined number of sheets. Further, the toner particles electrostatically aggregated at the nip portion between the toner layer regulating member and the developer carrying member are clogged, and streaks are generated. Conversely, if the ratio of Ψ / φ is greater than 2.8, the toner adheres to and remains in the dead space in the container or on the slope of the container where the stirring does not reach, so that the toner may not be supplied to the developer carrier. Ding may occur.

Furthermore, the amount of toner remaining in the cartridge at the end of printing can be controlled by simultaneously defining the slope angle θ of the developing container and the ratio Ψ / φ of the contact angle between the slope of the developing container and the toner, thereby reducing the number of times of cartridge swing. Further, it is possible to provide a pseudo no-shake function to the cartridge. For example, in a small printer in which the cost of the stirring member and the mechanism cannot be reduced, the cartridge swing may be performed many times and the maintenance load on the user may increase. This is because, even if the interaction between the toner and the surface of the developer container is small, if the circulation in the developer container is insufficient, the toner in the developer container receives a lot of triboelectric charge due to agitation and a toner that receives a small amount. This is because, as the amount of remaining toner decreases, the toner group that is smoothly supplied to the developer carrier and the other toner group do not, and the distribution of the amount of toner remaining near the developer carrier occurs. Therefore, by simultaneously defining θ and Ψ / φ, it is possible to correct the unevenness of the toner amount distribution and to smoothly print until the end of the life of the cartridge without shaking the cartridge itself to correct the unevenness. Become.

If the ratio is outside the above range, the desired effect cannot be obtained.

Hereinafter, the toner of the present invention having the above-described structure will be specifically described step by step.

First, FIG. 1 is a schematic diagram of a basic configuration of an image forming apparatus to which an image forming method using the toner of the present invention is applied.

The apparatus shown in FIG. 1 rotates a photosensitive drum 1 serving as an electrostatic image carrier, and is driven by the rotation of the photosensitive drum 1 so that a charging member pressed against the surface of the photosensitive drum 1 is pressed. Is rotated as the charging roller 2. A charging bias is applied to the charging roller 2 from a charging bias applying unit (not shown), whereby the surface of the photosensitive drum 1 is primarily charged. The surface of the primary charged photosensitive drum 1 is irradiated with laser light from the exposure device 3 to form an electrostatic charge image. The electrostatic image formed on the surface of the photosensitive drum 1 is developed by the above-mentioned developing means to form a toner image. The toner image formed on the photoreceptor drum 1 is transferred onto the transfer material P by the transfer unit 5, and includes, for example, a heated fixing roller 6a and a pressure roller 6b pressed against the fixing roller.
Is applied to the transfer material P by applying heat and pressure. The transfer residual toner remaining on the surface of the photoconductor drum 1 after the primary transfer is removed by a cleaning member 7 such as a cleaning blade in contact with the surface of the photoconductor drum 1 and cleaning of the surface of the photoconductor drum 1 is performed. Done. The image forming process after the above-described primary charging is repeatedly performed on the cleaned photosensitive drum 1 again.

FIG. 1 is the most basic configuration diagram of an image forming apparatus used in the image forming method of the present invention. In addition to the above-described developing means, a toner transport roller for supplying toner to a developer carrier, In order to transfer the toner image formed on the electrostatic image carrier 1 to the transfer material P, an intermediate transfer body for temporarily transferring the toner image from the electrostatic image carrier 1 may be used. Used.

Here, the developing means carries a toner,
A rotatable developer carrier 4 for transporting to a development area,
It is configured to have at least a toner layer thickness regulating member means 4a elastically pressed on the developer carrying member via a toner layer.

Next, the process cartridge used in the above-described image forming apparatus will be described. The process cartridge is detachable from the image forming apparatus, and includes a developer carrier 4, a toner layer regulating unit 4a, a toner container 12, and a stirring unit 1.
And a photosensitive unit 1 serving as a latent image carrier, a charging roller 2 serving as a charging unit provided around the photosensitive drum, and a cleaning unit 7 for cleaning the surface of the photosensitive drum. It is composed of a C unit 14 to be enclosed.

When this process cartridge reaches the end of its life, the user can easily replace it. The life of the process cartridge is usually the time when the toner is consumed and becomes insufficient, and an image white spot occurs.

The developer container used in the present invention can have any shape depending on the machine. In addition, a commercially available container forming apparatus can be used for the method of forming the container. Further, in order to improve the toner transportability, a chemical treatment may be performed on the inner wall surface or the inclined surface of the developer container, or a sheet or the like whose surface is treated may be added to the inclined portion.

The developer container used in the present invention is made of at least a molding resin, and may contain functional fillers such as conductive fine powder particles, filler particles, pigments and the like according to the purpose.

Examples of the molding resin include styrene resins, vinyl resins, polyethersulfone resins, polycarbonate resins, polyphenylene oxide resins, polyamide resins, fluororesins, cellulose resins, and acrylic resins. ; Epoxy resins, polyester resins, alkyd resins, phenolic resins, melamine resins,
A thermosetting resin or a photosetting resin such as a polyurethane resin, a urea resin, a silicone resin, and a polyimide resin, or a blend resin using two or more kinds of the above resins can be used.

Contact angle φ of developer storage container slope with water
Is preferably 40 ° to 90 °. Within the above range, the effect of moisture due to moisture absorption on the container slope can be reduced, and a small amount of water can be supplied to the toner particles from the container slope,
Or, the electrostatic adhesion of the toner particles to the inner surface of the container can be suppressed, so that the toner circulation is improved.

The developer carrier that can be used in the present invention contains at least conductive fine particles in a film-forming polymer material (resin).

The conductive fine particles are preferably crystalline graphite or crystalline graphite and carbon fine particles.

The crystalline graphite used in the present invention is:
It can be roughly classified into natural graphite and artificial graphite. Artificial graphite is obtained by solidifying pitch coke with tar pitch or the like.
Once fired at about 200 ° C, put in a graphitization furnace,
By processing at a high temperature of about 0 ° C., carbon crystals grew and turned into graphite. Natural graphite is completely graphitized by geothermal heat and high pressure underground for a long time.
Produce from underground. These graphites have various excellent properties, and have wide industrial applications. Graphite is a dark gray to black glossy, very soft, lubricious carbon crystal that is used for pencils and other materials, and has heat resistance and chemical stability, so lubrication, fire resistance, electrical materials, etc. It is used in powder, solid, and paint forms. The crystal structure is classified into a hexagonal system and a rhombohedral system, and has a complete layer structure. Regarding electrical properties, free electrons exist between carbon and carbon bonds, and are good conductors of electricity. In the present invention, either natural or artificial graphite can be used. The particle size of the graphite used is preferably about 0.5 to 20 μm.

As the carbon fine particles, conductive amorphous carbon can be used. The conductive amorphous carbon is generally defined as "an aggregate of crystallites formed by burning or thermally decomposing a compound containing hydrocarbons or carbon in an insufficient air supply". In particular, it is excellent in electric conductivity, and is widely used because it can be filled with a polymer material to impart conductivity, or a certain degree of conductivity can be obtained by controlling the amount of addition. The particle diameter of the conductive amorphous carbon used in the present invention is preferably from 10 to 80 nm, more preferably from 15 to 40 nm.

Examples of the film-forming polymer material include thermoplastic resins such as styrene resin, vinyl resin, polyether sulfone resin, polycarbonate resin, polyphenylene oxide resin, polyamide resin, fluororesin, cellulose resin, and acrylic resin. Resin: A thermosetting resin such as an epoxy resin, a polyester resin, an alkyd resin, a phenol resin, a melamine resin, a polyurethane resin, a urea resin, a silicone resin, and a polyimide resin or a photocurable resin can be used. Among them, silicone resin,
Releasable material such as fluororesin, or excellent in mechanical properties such as polyethersulfone resin, polycarbonate resin, polyphenylene oxide resin, polyamide resin, phenol resin, polyester resin, polyurethane resin and styrene resin Is more preferred.
These resins are appropriately selected in consideration of the charging property to the toner.

The toner layer thickness regulating member used in the present invention may be formed by urethane rubber, silicone rubber, or a resin having elasticity as a blade, or a blade made of metal or the like holding a chip-shaped resin at the tip thereof. One that is in contact with or pressed against the moving direction in the forward or reverse direction is used. Preferably, the blade is pressed against the moving direction of the developer carrying member in the opposite direction. At this time, the contact pressure of the blade against the developer carrier is preferably 9.8 N / m or more (10 g / cm or more) in linear pressure, and more preferably 19.6 to 49 N / m (20 to 50 g / cm).
cm).

A charging step that can be used in the present invention;
In the transfer process, (a) a method that does not contact with the electrostatic image holder using a corona discharger (a) a contact type of any type such as a roller type, a belt type, a combination of a belt and an electrode blade, and the like. Any of them can be used.

As the electrostatic image carrier of the present invention, there are an amorphous silicon photosensitive member and an organic photosensitive member, and an organic photosensitive member is preferably used.

The organic photoreceptor may be of a so-called single layer type, in which the photosensitive layer contains a charge generating substance and a substance having charge transporting properties in the same layer, and a function comprising the charge transporting layer and the charge generating layer as components. It may be a separate type photoreceptor. A laminated photoreceptor having a structure in which a charge generation layer and a charge transport layer are laminated on a conductive substrate in this order is one of preferred examples.

That is, in the image forming method of the present invention, the matching of the toner of the present invention is particularly effective for an organic photoconductor in which the surface of the electrostatic image carrier is an organic compound such as a resin. That is, the organic photoreceptor is shaved by a contact member such as a cleaning blade. When the organic photoreceptor is combined with the toner of the present invention, the shaving of the organic photoreceptor is reduced by the interposition of a particle layer deposited on the cleaning blade nip.
Further, since the release of the hydrophobic inorganic fine powder due to durability is small, it is possible to prevent the occurrence of fusion and filming caused by the release.

Further, in the present invention, it is preferable to have a cleaning step for removing the toner remaining on the surface of the electrostatic image carrier after the transfer step.

As the cleaning method, blade cleaning, mag brush cleaning, fur brush cleaning, roller cleaning, and combinations thereof can be used. Particularly, blade cleaning is preferable.

In blade cleaning, urethane rubber, silicone rubber, or elastic resin is used as a blade, or a blade made of metal or the like with a tip-shaped resin held at the tip thereof is moved in the forward direction or the moving direction of the photoconductor. It is known as abutting or pressing in the opposite direction. Preferably, the blade is pressed against the moving direction of the photoreceptor in the opposite direction. At this time, the contact pressure with the blade against the photoconductor is 19.6 N / m or more in linear pressure (2
0 g / cm or more), and more preferably 29.
4 to 78.4 N / m (30 to 80 g / cm).

Since the toner of the present invention not only provides an appropriate friction but also has excellent releasability and lubricity, it not only exhibits good cleaning properties by blade cleaning, but also makes it possible to bring the blade into contact with the photoreceptor. It is hard to be scratched and hard to cut. On the other hand, fusion, filming, and the like hardly occur.

In the fixing step of the present invention, a heating and pressing roll fixing device or a fixedly supported heating element is brought into pressure contact with the heating element, and the transfer material is brought into close contact with the heating element via a film. A fixing unit that heats and fixes the toner with the pressing member can be used.

The surface of the fixing roller or the fixing film comes into contact with the surface of the toner particles on the unfixed image, and receives a friction history through the durability. The toner having abrasive power is magnetic material particles protruding from the toner surface, or external additive particles or free external additive particles having low adhesion on the toner surface. By combining with the toner of the present invention, abrasion on the surface of the fixing roller or the fixing film can be reduced, and image defects such as black spots due to surface roughness and scratches can be reduced.

The transfer material that can be used in the present invention may be an intermediate transfer belt or an intermediate transfer member such as the same belt, in addition to commercially available paper and OHT.

Next, the image forming toner used in the present invention will be described in detail.

The toner used in the present invention has at least toner particles and a hydrophobic inorganic fine powder.
The toner contains at least a binder resin, magnetic particles and wax, and the contact angle ψ of the toner with water is 90 ° to 130 °.
° is preferred. If the angle is smaller than 90 °, the amount of toner adhering to the wall surface of the developer container increases, and the number of times of cartridge swinging increases. If it is larger than 130 °,
It is easy to charge up due to frictional charging between toner particles, which affects toner circulation.

As the binder resin for the toner used in the present invention, polyester resin, vinyl resin, epoxy resin and the like can be used.
A vinyl resin or a mixed resin of both is more preferable in terms of fixing characteristics and developing characteristics.

The following are examples of the monomer of the polyester resin used in the present invention.

As the alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and (a)
A bisphenol derivative represented by the formula:

[0060]

Embedded image

[0061]

Embedded image And the like.

The divalent carboxylic acid containing 50 mol% or more of the total acid component includes phthalic acid, isophthalic acid,
Benzenedicarboxylic acids such as terephthalic acid and phthalic anhydride or anhydrides thereof; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof, and further substituted with alkyl groups having 6 to 18 carbon atoms Succinic acid or its anhydride; and dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid.

Further, polyhydric alcohols such as glycerin, pentaerythritol, sorbit, sorbitan, and oxyalkylene ether of novolak phenol resin; trimellitic acid, pyromellitic acid,
Examples include polyvalent carboxylic acids such as benzophenonetetracarboxylic acid and its anhydride.

The polyester unit of the binder resin is preferably crosslinked with a trivalent or higher polyhydric carboxylic acid or polyhydric alcohol. The crosslinking components include trimellitic anhydride, benzophenonetetracarboxylic acid and pentaerythrium. Stall and oxyalkylene ether of a novolak type phenol resin are preferred.

The polyester resin thus obtained has a glass transition temperature (Tg) of from 40 to 90 ° C., preferably from 45 to 8 ° C.
5 ° C., and a number average molecular weight (Mn) of 1,000 to 50,
000, preferably 1,500 to 20,000, and a weight average molecular weight (Mw) of 3,000 to 100,000, preferably 40,000 to 90,000.

Examples of the vinyl monomer for producing the vinyl resin include the following. For example, styrene, o-methylstyrene, m-methylstyrene,
p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert Styrenes such as -butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene and derivatives thereof; ethylene, propylene, butylene , Ethylenically unsaturated monoolefins such as isobutylene; unsaturated polyenes such as butadiene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl acetate, vinyl propionate and vinyl benzoate. Vinyl ester acid such as methyl methacrylate, ethyl methacrylate Propyl methacrylate, n- butyl methacrylate, isobutyl methacrylate, n- octyl, dodecyl methacrylate, 2
Α-methylene aliphatic monocarboxylic esters such as ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid Acrylic esters such as isobutyl, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate;
Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole,
N-vinyl compounds such as N-vinylpyrrolidone; vinylnaphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide; esters of the aforementioned α, β-unsaturated acids and diesters of dibasic acids No.

Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride Unsaturated dibasic acid anhydrides such as those; methyl maleate half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, methyl itaconate Half esters of unsaturated dibasic acids such as half ester, methyl alkenyl succinate half ester, methyl fumarate half ester and methyl half mesaconic acid; unsaturated dibasic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; Acid, methacrylic acid, crotonic acid, such as cinnamic acid alpha, beta-unsaturated acid; crotonic acid anhydride, such as alpha of cinnamic acid anhydride, beta-unsaturated acid anhydride, the alpha, beta
-Anhydrides of unsaturated acids and lower fatty acids; and monomers having a carboxyl group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, acid anhydrides and monoesters thereof. Furthermore, 2-
Acrylic acid or methacrylic acid esters such as hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; 4
-(1-hydroxy-1-methylbutyl) styrene, 4
And monomers having a hydroxy group such as-(1-hydroxy-1-methylhexyl) styrene.

Further, if necessary, the polymer may be crosslinked with a crosslinking monomer as exemplified below.

Aromatic divinyl compounds, for example, divinylbenzene, divinylnaphthalene, etc .; diacrylate compounds linked by an alkyl chain; for example, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol Diacrylate,
1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and acrylates of the above compounds replaced with methacrylates; diacrylate compounds linked by an alkyl chain containing an ether bond , Such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds instead of methacrylate Diacrylate compounds linked by a chain containing an aromatic group and an ether bond, for example, polyoxyethylene (2) -2,2-bis ( - hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,
2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylates of the above compounds with methacrylates; further, polyester-type diacrylate compounds, for example, trade name MANDA (Nippon Kayaku) . As multifunctional crosslinking agents, pentaerythritol acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and acrylates of the above compounds to methacrylate Alternatives; triallyl cyanurate, triallyl trimellitate; and the like.

These cross-linking agents can be used in combination with other monomer components 10
It is preferably used in the range of 0.01 to 10% by mass (more preferably 0.03 to 5% by mass) with respect to 0% by mass.

Among these crosslinkable monomers, those which are preferably used in the binder resin from the viewpoint of fixability and anti-offset properties include an aromatic divinyl compound (particularly divinylbenzene), an aromatic group and an ether bond. And diacrylate compounds linked by a chain.

Examples of the polymerization initiator used for producing the vinyl copolymer include, for example, 2,2′-azobisisobutyronitrile and 2,2′azobis (4-methoxy-2,4-dimethyl Valeronitrile), 2,2'-azobis (-2,4-dimethylvaleronitrile), 2,2 '
-Azobis (-2methylbutyrotolyl), dimethyl-
2,2'-azobisisobutyrate, 1,1'azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane ), 2-phenylazo 2,4-dimethyl-4-methoxyvaleronitrile,
Ketone peroxides such as 2,2′-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetylacetone peroxide and cyclohexanone peroxide; 2,2-bis (t-butylperoxy) butane, t-butylhydro Peroxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α, α-bis ( t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-
Trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-n-propylperoxydicarbonate, di-2-ethoxyethylperoxide Oxycarbonate, di-methoxyisopropylperoxydicarbonate, di- (3-methyl-3-methoxybutyl) peroxocarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate , T
-Butyl peroxy neodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxy laurate, t-butyl peroxy benzoate, t
-Butyl peroxyisopropyl carbonate, di-t
-Butylperoxyisophthalate, t-butylperoxyallyl carbonate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate and the like. Can be

The vinyl binder resin has a glass transition temperature (Tg) of 45 to 80 ° C., preferably 55 to 70 ° C., and a number average molecular weight (Mn) of 2,500 to 50,000.
Weight average molecular weight (Mw) 10,000-1,000,000
00 is preferred.

In the present invention, a homopolymer or copolymer of a vinyl monomer, polyester, polyurethane, epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, An aromatic petroleum resin or the like can be used by mixing it with the binder resin described above as necessary.

When two or more resins are mixed and used as a binder resin, as a more preferred form, those having different molecular weights are preferably mixed at an appropriate ratio.

In the present invention, a metal-containing compound which causes a crosslinking reaction with a resin binder may be contained.

As the reactive metal compound used in the present invention, those containing the following metal ions can be used. Suitable monovalent metal ions include Na ⁺ , Li ⁺ , Cs ⁺ , Ag ⁺ , H
g ⁺ , Cu ^{+ and the} like.
e ²⁺ , Mg ²⁺ , Ca ²⁺ , Hg ²⁺ , Sn ²⁺ , Pb ²⁺ , Fe
²⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ and the like. The trivalent ions include Al ³⁺ , Sc ³⁺ , Fe ³⁺ , Co ³⁺ , and N ³
i ³⁺ , Cr ³⁺ and the like. Among the compounds containing metal ions as described above, the more decomposable, the better the results. This is presumed to be due to the fact that the metal ion in the compound is more easily bonded to the carboxyl group in the polymer by the thermal decomposition in the decomposable one.

Among the reactive metal compounds, the organometallic compounds are excellent in compatibility and dispersibility with the polymer, and the crosslinking by the reaction with the metal compound proceeds more uniformly in the polymer, so that more excellent results are obtained. . Among the reactive organometallic compounds as described above, those containing an organic compound which is particularly highly vaporizable and sublimable as a ligand and a counter ion are useful.
Among the organic compounds that form a ligand or a counter ion with a metal ion, those having the above properties include, for example, salicylic acid, salicylamide, salicylamine, salicylaldehyde, salicylosalicylic acid, ditert-
Salicylic acid and its derivatives such as butylsalicylic acid; for example, β such as acetylacetone and propionacetone
-Diketones; for example, low molecular weight carboxylate such as acetate and propionic acid.

The amount of the metal compound used in the present invention is:
0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass is desirable per 100 parts by mass of the binder resin.

In the present invention, in order to improve the hydrophobicity of the toner particles, one or more waxes are preferably contained in the toner.

For example, aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax;
Oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; waxes mainly containing fatty acid esters such as carnauba wax, sasol wax, montanic acid ester wax, and deacidification Fatty acid esters such as carnauba wax are partially or entirely deoxidized. In addition, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and vinaric acid, stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, and seryl alcohol And polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide and lauric acid amide;
Saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide; ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, N, N'-dioxide Unsaturated fatty acid amides such as rail adipamide and N, N'-dioleyl sebacamide; aromatic bisamides such as m-xylene bisstearic acid amide and N, N'-distearyl isophthalic amide; Grafting of fatty acid metal salts such as calcium phosphate, calcium laurate, zinc stearate, and magnesium stearate (commonly referred to as metal soaps), and aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid Transformed And waxes, also partial esters of fatty acids with polyhydric alcohols such as behenic acid monoglyceride, also like methyl ester compounds having hydroxyl groups obtained by and hydrogenated vegetable oils.

The wax which is particularly preferably used in the present invention comprises a hydrocarbon having a straight-chain alkyl group having a small number of branches. Specifically, a wax obtained by radical polymerization of alkylene under high pressure or polymerization of Zylene under low pressure by a Ziegler catalyst is used. Alkylene polymer having a high molecular weight, an alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer,
A wax such as a synthetic hydrocarbon obtained from the distillation residue of hydrocarbons obtained from the synthesis gas composed of carbon monoxide and hydrogen by the Age method or by hydrogenation thereof is preferred. Further, those obtained by separating a hydrocarbon wax by use of a press sweating method, a solvent method, vacuum distillation or a separation crystallization method are more preferably used. Hydrocarbons as a parent are
Synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide-based catalyst (often a multi-component system of two or more types),
For example, hydrocarbons having up to several hundred carbons, ethylene, etc., obtained by the Zintall method, the hydrochol method (using a fluidized catalyst bed), or the Aage method (using a fixed catalyst bed), which produces a large amount of waxy hydrocarbons Hydrocarbons obtained by polymerizing the above alkylene with a Ziegler catalyst are preferred because they are linear hydrocarbons having a small number of branches, a small number of branches and a long saturation. Particularly, a wax synthesized by a method not based on the polymerization of alkylene is preferable in view of its molecular weight distribution.

In the present invention, the molecular weight distribution of the wax is in the range of 400 to 2400, preferably 450 to 2400.
000, particularly preferably 500 to 1600. By providing such a molecular weight distribution, the toner can have favorable thermal characteristics.

In the present invention, fine dispersion of the wax in the binder resin when the toner is melted is prevented, and the domain diameter and the total number of the wax exposed on the surface of the toner particles are controlled to improve the fluidity of the toner. Considering that, the wax has an acid value of 0 to 1 mgKOH / g and a hydroxyl value of 0 to 1 mgKOH / g.
It is preferably KOH / g.

The amount of the wax used in the present invention is desirably 0.1 to 30 parts by mass, preferably 5 to 20 parts by mass, per 100 parts by mass of the binder resin.

The coloring agent used in the present invention includes one component,
Regardless of the two components, carbon black, titanium white,
Any pigment and / or dye can be used, and the magnetic material may also serve as the colorant.

Examples of the magnetic material include iron oxides such as magnetite, maghemite, and ferrite, and iron oxides containing other metal oxides; metals such as Fe, Co, and Ni; or these metals and Al, Co, Cu, Pb, Mg, N
i, Sn, Zn, Sb, Be, Bi, Cd, Ca, M
Alloys with metals such as n, Se, Ti, W, and V, and mixtures thereof, and the like.

As the magnetic material, conventionally, triiron tetroxide (F
e ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), yttrium iron oxide (Y ₃ Fe
₅ O ₁₂ ), cadmium iron oxide (CdFe ₂ O ₄ ), gadolinium iron oxide (Gd ₃ Fe ₅ O ₁₂ ), copper iron oxide (CuFe
₂ O ₄ ), lead iron oxide (PbFe ₁₂ O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), iron neodymium oxide (NdFe ₂ O ₃ ),
Barium iron oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnFe
₂ O ₄ ), iron oxide lanthanum (LaFeO ₃ ), iron powder (F
e), cobalt powder (Co), nickel powder (Ni) and the like are known. In the present invention, the above-mentioned magnetic materials can be used alone or in combination of two or more kinds. Particularly preferred magnetic materials are fine powders of iron tetroxide or γ-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.1 to 2
At about μm, the magnetic properties when applying 795.8 kA / m (10 k Oersted) show a coercive force of 1.6 to 12 kA / m.
(20-150 Oersted), saturation magnetization 50-200
Am ² / kg (preferably 50~100Am ² / kg),
Those having a residual magnetization of ^{2 to 20} Am ² / kg are desirable.

The magnetic material 1 was added to 100 parts by mass of the binder resin.
It is preferable to use 0 to 200 parts by mass, preferably 20 to 150 parts by mass.

When the toner of the present invention is used as a color toner, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I.
I. Modant Red 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I.
Modant Blue 7, C.I. I. Direct Green 6,
C. I. Basic Green 4, C.I. I. Basic Green 6 and the like. Examples of pigments include: graphite, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, red-mouthed graphite, molybdenum orange, permanent orange GT
R, pyrazolone orange, benzidine orange G, cadmium red, permanent red 4R, watching red calcium salt, eosin lake, brilliant carmine 3B, manganese purple, fast violet B, methyl violet lake, navy blue, cobalt blue, alkaline blue lake, Victoria Blue Lake, Phthalocyanine Blue, First Sky Blue, Indanthrene Blue BC, Chrome Green, Chromium Oxide, Pigment Green B, Malachite Green Lake, Final Yellow Green G and the like.

The amount of the colorant used is 0.1 to 60 parts by mass, preferably 0.5 to 60 parts by mass, based on 100 parts by mass of the binder resin.
50 parts by mass.

Considering that the toner of the present invention is imparted with sufficient hydrophobicity to the toner particles to simultaneously suppress the fading and reduce the number of times of cartridge swing, it is preferable to use a hydrophobic inorganic fine powder. preferable.

Examples of the hydrophobic inorganic fine powder that can be used in the present invention include fine powders of inorganic oxides and hydrophobicized products such as inorganic carbonate compounds. In particular, hydrophobic silica fine powder, hydrophobic titanium oxide fine powder and the like are preferably used.

In the present invention, it is preferable to treat the inorganic fine powder with an organosilicon compound, for example, a silane coupling agent, in order to improve the hydrophobicity.

Examples of the silane coupling agent used for the hydrophobizing treatment include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allyl Phenyldichlorosilane, benzyldimethylchlorosilane,
Bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan,
Triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and one molecule For example, a dimethylpolysiloxane containing 2 to 12 siloxane units per unit and a hydroxyl unit containing a hydroxyl group bonded to Si is located at one terminal unit.
These are used alone or as a mixture of two or more.

The treatment of the silica fine powder with the silane coupling agent may be performed by a dry treatment in which a vaporized silane coupling agent is reacted with a ground silica fine powder by stirring or the like, or a silane coupling agent in which silica is dispersed in a solvent. The treatment can be carried out by a generally known method such as a wet method in which a coupling agent is dropped.

In the present invention, treatment with an organosilicon compound, for example, silicone oil or the like is preferable for improving hydrophobicity. Preferred silicone oils include:
The viscosity at 25 ° C. is about 30 to 1000 mm ² / s
Is used.

In the case of the negatively chargeable silica fine powder, for example, dimethyl silicone oil, alkyl-modified silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, fluorine-modified silicone oil and the like are preferable.

In the case of positively chargeable silica, it is preferable to treat with a silicone oil having an organo group having at least one nitrogen atom in a side chain, or a nitrogen-containing silane coupling agent.

In the method of treating silicone oil, for example, inorganic fine powder treated with a silane coupling agent and silicone oil may be directly mixed using a mixer such as a Henschel mixer. Alternatively, it may be prepared by dissolving or dispersing a silicone oil in an appropriate solvent, mixing with a base silica fine powder, and removing the solvent. In the present invention, the hydrophobizing treatment is imparted by chemically treating with an organic silicon compound or the like which reacts or physically adsorbs with the inorganic fine powder. As a preferred method, after treating the inorganic fine powder with a silane coupling agent,
Alternatively, a method of treating with a silane coupling agent and at the same time with an organosilicon compound such as silicone oil may be used. Specifically, the method includes preparing an inorganic fine powder by treating it with dimethyldichlorosilane, then treating it with hexamethyldisilazane, and then treating it with silicone oil.

It is particularly preferred that the inorganic fine powder is treated with two or more silane coupling agents as described above, and then treated with oil since the degree of hydrophobicity can be effectively increased.

Among the hydrophobic inorganic fine powders, those having a specific surface area of 30 m ² / g or more (particularly 50 to 400 m ² / g) by nitrogen adsorption measured by the BET method are preferably used.

The hydrophobic inorganic fine powder of the present invention controls the adhesion of the inorganic fine powder itself while imparting sufficient hydrophobicity to the inorganic fine particles, and suppresses the formation of lumps (so-called fine powder lumps). In view of this, in consideration of avoiding development streaks, fusing, and the like, the carbon content is preferably 4.5 to 12.0% by weight.

The carbon content is determined by the following method. The carbon contained in the surface hydrophobic group of the inorganic fine powder is 11
After pyrolysis into CO ₂ at 00 ° C. in an oxygen atmosphere, the carbon content of the silica was analyzed by a trace carbon analyzer (WMIA-110, manufactured by Horiba).

An external additive other than silica fine powder or titanium oxide fine powder may be added to the toner of the present invention, if necessary. For example, a lubricant such as Teflon (registered trademark), zinc stearate, and polyvinylidene fluoride, among which polyvinylidene fluoride is preferable. Or cerium oxide,
Abrasives such as silicon carbide and strontium titanate, among which strontium titanate are preferred. Alternatively, for example, a fluidity-imparting agent such as titanium oxide and aluminum oxide, particularly a hydrophobic agent is preferable. A small amount of an anti-caking agent, or a conductivity-imparting agent such as carbon black, zinc oxide, antimony oxide, or tin oxide, or white and black fine particles of opposite polarity can also be used as a developability improver. If necessary, resin fine particles may be added internally or externally to such an extent that the fixability is not impaired. For example, vinyl-based resin fine particles are produced by an emulsion polymerization method, a spray drying method, or the like. Preferably, styrene,
Acrylic acid, 2-ethylhexyl acrylate, methyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, N-methyl-N-phenylethyl methacrylate, diethylaminoethyl methacrylamide, dimethylaminoethyl methacrylamide, 4-vinylpyridine, 2-vinylpyridine Resin particles obtained by copolymerizing a vinyl monomer such as above or a mixture of these monomers by an emulsion polymerization method are preferred.

The resin fine particles, inorganic fine powder or hydrophobic inorganic fine powder mixed with the toner is used in an amount of 0.1 to 5 parts by mass (preferably 0.1 to 3 parts by mass) based on 100 parts by mass of the toner. Is good.

In the toner used in the present invention, it is preferable that a charge control agent is blended (internally added) with toner particles or mixed (externally added) with toner particles. The charge control agent makes it possible to control the charge amount adapted to other systems such as a developing system. In particular, in the present invention, this makes it possible to optimize the charge amount of the toner on the transfer material. And good transferability is obtained.

When the toner of the present invention has a negative triboelectric property,
Examples of the charge control agent include organometallic complexes, metal salts, chelate compounds such as monoazo metal complexes, acetylacetone metal complexes, hydroxycarboxylic acids, metal complexes, polycarboxylic acid metal complexes, and polyol metal complexes. Also, metal complex salts of carboxylic acids, carboxylic anhydrides,
Condensates of carboxylic acid derivatives such as esters, aromatic compounds, bisphenols, phenol derivatives such as calixarenes, copolymers of styrene / acrylic monomers and sulfonic acid-containing acrylamide monomers, etc. No.

The negative charge control agent for the dye compound is represented by, for example, the following general formula.

[0111]

Embedded image [Wherein, M represents a coordination center metal, and Cr, C
o, Ni, Mn, Fe and the like. Ar is an aryl group, such as a phenyl group or a naphthyl group, which may have a substituent. In this case, as a substituent,
Examples include a nitro group, a halogen group, a carboxyl group, an anilide group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group. X, X ', Y and Y' are -O-, -CO-, -NH
-Or -NR- (R is an alkyl group having 1 to 4 carbon atoms)
It is. A ⁺ represents hydrogen, sodium ion, potassium ion, ammonium ion, or aliphatic ammonium ion. ]

As a more effective charge control agent usable in the present invention, a copolymer of a styrene / acrylic monomer and a sulfonic acid-containing acrylamide monomer is preferably used. This copolymer is preferable in terms of compatibility and dispersibility in a toner to which a large amount of wax is added, and can improve the total toner performance.

The styrene / acrylic monomer used in the charge control agent is appropriately selected from the above-mentioned vinyl monomers for producing the vinyl polymer.

The sulfonic acid-containing acrylamide monomers include 2-acrylamidopropanesulfonic acid,
2-acrylamide-n-butanesulfonic acid, 2-acrylamide-n-hexanesulfonic acid, 2-acrylamide-n-octanesulfonic acid, 2-acrylamide-
n-dodecanesulfonic acid, 2-acrylamide-n-tetradecanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, 2-acrylamide-2-phenylpropanesulfonic acid, 2-acrylamide-2,
2,4-trimethylpentanesulfonic acid, 2-acrylamido-2-methylphenylethanesulfonic acid, 2-acrylamido-2- (4-chlorophenyl) propanesulfonic acid, 2-acrylamido-2-carboxymethylpropanesulfonic acid, 2- Acrylamide-2- (2-
Pyridyl) propanesulfonic acid, 2-acrylamide-
1-methylpropanesulfonic acid, 3-acrylamide-
3-methylbutanesulfonic acid, 2-methacrylamide-
Examples thereof include n-decanesulfonic acid and 2-methacrylamide-n-tetradecanesulfonic acid. Preferably, 2-acrylamido-2-methylpropanesulfonic acid is used.

The polymerization initiator used for synthesizing the charge control resin is appropriately selected from the initiators used for producing the above-mentioned vinyl copolymer. Preferably, a peroxide initiator is used. The method for synthesizing the charge control resin is not particularly limited, and any method such as solution polymerization, suspension polymerization, or bulk polymerization can be used.However, solution polymerization in which an organic solvent containing a lower alcohol is copolymerized is used. preferable.

The copolymerization ratio of the styrene / acrylic monomer and the sulfonic acid-containing acrylamide monomer is 98:98 in consideration of stabilizing charging characteristics and environmental characteristics.
2 to 80:20 and a weight average molecular weight of 2000 to 1
Preferably, the polymer is 5000.

When the toner of the present invention has a positive triboelectric property, the charge control agent may be modified with nigrosine, a fatty acid metal salt, or the like;
Onium salts such as quaternary ammonium salts such as hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate and their analogs such as phosphonium salts, and lake pigments thereof, triphenylmethane dyes and these lake pigments ( Lake agents include phosphotungsten molybdic acid, tannic acid, lauric acid,
Gallic acid, ferricyanic acid, ferrocyanide, etc.), metal salts of higher fatty acids; diorganotin oxides, such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; diorganotin borates, such as dibutyltin borate; guanidine compounds, imidazole Compounds can be used alone or in combination of two or more. Among these, a triphenylmethane compound and a quaternary ammonium salt whose counter ion is not halogen are preferably used. Also, the general formula

[0118]

Embedded image [In the formula, R ₁ represents H, CH ₃ , and R ₂ , R ₃ represents a substituted or unsubstituted alkyl group (preferably, C1 to C4). And a copolymer with a polymer monomer such as styrene, acrylate or methacrylate described above. The charge control agent in these cases also has an action as (all or part of) the binder resin.

One or more of the above can be contained. The content of the charge control agent is set to 0.1 to 100 parts by mass of the binder resin of the toner in consideration of controlling the fluidity and the amount of charge of the toner to avoid generation of fog and low concentration.
To 5 parts by mass, particularly preferably 0.2 to 3 parts by mass.

The toner particles used in the present invention may have a weight average particle diameter in consideration of controlling the fluidity of the toner and the circulating property of the toner in the developing container to avoid fading and development streaks. Is preferably 5 to 12 μm (more preferably 5 to 9 μm).

Further, even when the developer carrier of a small diameter is advanced quickly, the toner of the present invention is transferred to the developer carrier on the slope for transferring from the inside of the developer container to the developer carrier side. The fluidity index A is preferably 5 to 70% from the viewpoint that the toner is smoothly supplied, spreads in the longitudinal direction near the developer carrying member, and a good image can be obtained even near the toner shortage.

To prepare the magnetic toner of the present invention, a binder resin, a magnetic substance (and a colorant), a charge control agent or other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and the mixture is kneaded. Melting, kneading and kneading using a hot kneader such as an extruder to make the resins compatible with each other, cooling and solidifying the melt-kneaded product, pulverizing the solidified product, classifying the pulverized product, and classifying the magnetic material of the present invention. A toner can be obtained. Other methods include dispersing the constituent materials in a binder resin solution and then spray drying to obtain a toner, or mixing a predetermined material with a monomer to form the binder resin and emulsifying the mixture. There is a method for producing a toner by a polymerization method in which a suspension is formed and then polymerized to obtain a toner. The toner according to the present invention may be a microcapsule toner composed of a core material and a shell material.

Further, the hydrophobic inorganic fine powder, other inorganic fine powder and the magnetic toner are sufficiently mixed by a mixer such as a Henschel mixer to obtain the toner of the present invention having an additive on the surface of the toner particles.

The following are generally used as toner production apparatuses, but are not limited thereto.

(1) Example of pulverizing apparatus for toner production Apparatus name Manufacturer Manufacturer Counterjet Mill Hosokawa Micron Micron Jet Hosokawa Micron IDS Mill Nippon Pneumatic Industries PJM Jet Pulverizer Nippon Pneumatic Industries Cross Jet Mill Awamoto Iron Works・ Ulmax Nisso Engineering ・ SK Jet O-Mill Seishin Company ・ Cryptron Kawasaki Heavy Industries ・ Turbo Mill Turbo Industries ・ Inomaiza Hosokawa Micron

(2) Example of mixing device for toner production Device name Manufacturer Henschel Mixer Mitsui Mining, Super Mixer Kawata, Ribo Cone Okawara Seisakusho, Nauta Mixer Hosokawa Micron, Spiral Pin Mixer Taiheiyo Kiko, Redige Mixer Matsubo, Turbulizer Hosokawa Micron・ Cyclomix Hosokawa Micron

(3) Classifier for toner production Name of manufacturer Manufacturer : Crassell Seishin Company Micron Classifier Seishin Company Spedic Classifier Seishin Company Turbo Classifier Nisshin Engineering Micron Separator Hosokawa Micron Turboplex (ATP) Hosokawa Micron-TSP Separator Hosokawa Micron-Elbow Jet Nippon Steel Mining-Dispersion Separator Nippon Pneumatic Industries-YM Micro Cut Yasukawa Shoji

(4) Example of kneading device for toner production Device name Manufacturer KRC Kneader Kurimoto Iron Works ・ Bus Co Kneader Buss ・ TEM Extruder Toshiba Machine ・ TEX twin screw kneader Japan Steel Works ・ PCM Kneader Ikekai Iron Works・ 3 roll mill Inoue Works ・ Mixing roll mill Inoue Works ・ Kneader Inoue Works ・ Kneedex Mitsui Mine ・ MS pressurized kneader Moriyama Works ・ Nidar Ruder Moriyama Works ・ Banbury Mixer Kobe Steel

(5) Example of sieve device for toner production Device name Manufacturer・ Ultrasonic Koei Sangyo ・ Resona Sieve Tokuju Works ・ Vibrasonic System Dalton ・ Soniclean Shinto Works ・ Gyro Shifter Tokuju Works ・ Circular vibrating sieve manufacturer・ Turbo screener Turbo industry ・ Mitaro shifter Makino Sangyo

The physical properties of the toner in the present invention are measured by various measuring instruments according to the methods corresponding thereto. The measuring methods are described below.

(1) Measurement of Contact Angle of Toner About 4 g of a sample was measured at 490000 kPa (5000 kg).
f / cm ² ) for about 1 minute to produce a flat molded product. Kyowa Interface Science Co., Ltd. contact angle meter (C
AX) according to the instruction manual and the contact angle of the plate-shaped molded product was measured using ion-exchanged water or commercially available purified water. Corners.

(2) Measurement of contact angle of developer carrier Using a contact angle meter (CA-X type, manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of the developer carrier was measured in the longitudinal direction according to the instruction manual. Five points and a total of 20 points in the circumferential direction were measured using ion-exchanged water or commercially available purified water, and the average value at the time of measurement was taken as the contact angle of the developer carrying member.

(3) Measurement of Developer Storage Container Slope Angle Each dimension of the developer storage container is determined by three-dimensional measurement, and after two-dimensionalization, the slope angle θ as shown in FIG. 2 is determined. Alternatively, after the developer container is cut vertically near the center in the longitudinal direction, the cross section may be measured using a measuring jig.

(4) Measurement of Fluidity Index (Agglomeration Degree) FIG. 3 is a schematic explanatory diagram of the measurement of the fluidity index. In the present invention, the fluidity index (aggregation degree) A of the toner was determined by the following method. Measuring device: Powder tester PT-N type (Hosokawa Micron Co., Ltd.) Measuring method: Based on the measurement of the degree of aggregation in the instruction manual attached to the powder tester PT-N type. Sieve opening 250 μm, 150 μm, 75 μm Amplitude (vibration displacement) 2.58 V Vibration time 15 s Sample amount 5.0 g

However, after the sample was allowed to stand overnight at 23 ° C. and 60% RH, the sample masses G1, G2 and G3 on the respective sieves before and after the test were measured with a measuring device in an environment of 23 ° C. and 60% RH. The fluidity index 求 め る is obtained by the following formula, and the value obtained by repeating the measurement five times and taking the arithmetic average is defined as A.

A = G1 + G2 + G3 G1 = (mass of toner on sieve with openings of 250 μm / 5.0)
× 100 G2 = (mass of toner on mesh 150 μm sieve / 5.0)
× 0.6 × 100 G3 = (mass of toner on mesh 75 μm sieve / 5.0) ×
0.2 × 100

(5) Measurement of Particle Size The particle size can be measured by various methods. In the present invention, Coulter Multisizer (manufactured by Coulter Co., Ltd.) is used. % NaCl aqueous solution is prepared. As the electrolytic solution, for example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measurement method, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and the measurement sample is further added to 0.002 to 0.002.
Add ~ 0.020 g. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the sample solution is added to a cell of the measuring device by a pipette or the like. In addition, using a 100 μm aperture as the aperture, a 2 μm
The volume and number of the toner were measured to calculate the volume distribution and the number distribution.

The weight average diameter D according to the present invention was determined from the weight standard average diameter (D4: the median value of each channel is a representative value for each channel) obtained from the volume distribution.

[0139]

The present invention will be described below with reference to production examples and examples. However, this does not limit the present invention in any way.

Example 1 Binder resin 100 parts by mass (styrene / n-butyl acrylate copolymer monomer ratio: 75:25, Mn: 9000, Mw: 150,000, Tg: 63 ° C., P1: 13000, P2 : 700,000)-Magnetic iron oxide 100 parts by mass (average particle size 0.2 µm)-Polyethylene 7 parts by mass-Monoazo iron complex salt 2 parts by mass After pre-mixing the above materials with a Henschel mixer, 130
Melt kneading was performed at 2 ° C. by a twin screw kneading extruder. After allowing the kneaded material to cool, coarsely pulverized by a cutter mill, pulverized using a fine pulverizer using shear stress, and further classified using an air classifier, the magnetic toner particles having a weight average particle diameter of 11.9 μm. I got

Further, 0.9% by mass of silica P1 (BET 200 m ^{2 /} g) shown in Table 2 was added to the magnetic toner, and externally added using a Henschel mixer to prepare a toner T1 shown in Table 1.

Tables 1 and 3 show the measurement results of various properties of the magnetic toner by the methods described above.

Using this externally added toner, a Canon laser beam printer LBP470 having the configuration shown in FIG.
Remodeling machine (toner carrier outer diameter 15mm, peripheral speed 65mm /
s, endurance of 5,000 sheets in a developing container at a slope angle of 70 ° and a contact angle of the slope of 30 ° at room temperature and normal humidity (23 ° C., 60% R).
H), and the image characteristics were evaluated by the following evaluation methods. As a result, the results shown in Table 3 were obtained.

During the endurance, a halftone image was produced at a rate of one out of 100 sheets, and the presence or absence of fading occurrence recognized in the sample was visually observed. ：: Not generated Δ: Fading seen on the back side of the image is slightly at the front end of the image, but disappeared in subsequent images, and there is no effect on the image. ×: Fading seen on the back side of the image is an image Appears in a band form from the leading edge to the trailing edge, causing image defects

The no-shake property was evaluated by the number of times the cartridge was shaken until the life of the cartridge was completed.
However, the term "life" here refers to a point in time when the image is blurred due to insufficient supply of the toner to the toner carrier, and the remaining toner amount in the developing container becomes 15 g. ：: When the cartridge swing is one or less Δ: When the cartridge swing is two or three times ×: When the cartridge swing is four or more times

The state of occurrence of streaks recognized in the sample during the running and the influence on the printout image were visually evaluated. ：: not generated Δ: streaks observed on the back side of the image are less than 5 points, and there is no effect on the image ×: streaks observed on the back side of the image are 10 points or more, causing image defects

<Examples 2 to 6> Toners were prepared in the same manner as in Example 1 except that the toner particle size and the type and amount of the external additive were changed.

Tables 1 and 3 show the measurement results of various physical properties of the toner by the methods described above.

Further, Example 1 was repeated using the toner, except that the settings of the developing container and the developer carrier were changed as shown in Table 3.
The same evaluation as described above was performed, and the results shown in Table 3 were obtained.

Example 7 The binder resin was a polyester resin [Mn: 3000, Mw: 52000, Tg: 64 ° C.,
P1: 3300, P2: 110,000], and the toner particle size and the type and amount of the external additive were changed to prepare a toner. Thus, a toner T7 in Table 1 was obtained.

Tables 1 and 3 show the measurement results of various physical properties of the toner by the methods described above.

Further, Example 1 was carried out using the toner except that the settings of the developing container and the developer carrier were changed as shown in Table 3.
The same evaluation as described above was performed, and the results shown in Table 3 were obtained.

Comparative Examples 1 to 3 Toners T8 to T9 shown in Table 1 were obtained in the same manner as in Example 1 except that the toner particle size and the type and amount of the external additive were changed. Tables 1 and 3 show the measurement results of various physical properties of the toner by the methods described above.

Further, Example 1 was repeated using the toner except that the settings of the developing container and the developer carrier were changed as shown in Table 3.
The same evaluation as described above was performed, and the results shown in Table 3 were obtained.

[0155]

[Table 1]

[0156]

[Table 2]

[0157]

[Table 3]

[0158]

As described above, by using the image forming toner and the image forming method of the present invention, it is possible to suppress the occurrence of fading and development streaks and to reduce the swing of the cartridge near the toner shortage. An image forming toner, an image forming method, and a process cartridge can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view of an image forming method and a process cartridge used in an embodiment of the present invention.

FIG. 2 is a schematic explanatory diagram of a developer container slope angle.

FIG. 3 is a schematic explanatory view of an apparatus for measuring a fluidity index (aggregation degree) of a toner.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 electrostatic image carrier (photosensitive drum) 2 charging member 3 exposure device 4 developer carrier (developing sleeve) 4 a toner layer thickness regulating member (developing blade) 5 transfer unit 6 fixing unit 6 a fixing roller 6 b pressure roller 7 cleaning Members 8a, 8b, 9a, 9b, 10a, 10b Conveying member 11 Developing unit 12, 12a Toner container 13 Toner stirring means 14 Cleaning unit (C unit) 15 Cleaner container 16 Sieve with opening 250 μm 17 Sieve with opening 125 μm 18 Eye Opening 75μm sieve 19 Shaking table T Toner P Transfer material L Exposure

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) G03G 15/08 501 G03G 9/08 101

Claims (17)

[Claims] 1. An image forming method, comprising: developing an electrostatic image by a developing unit having a toner to form a toner image on an electrostatic image carrier, wherein the developing unit develops the electrostatic image. For toner,
At least a developer accommodating container for accommodating the toner and a developer carrier for carrying and transporting the toner accommodated in the developing container, wherein the developer accommodating container contains the contained toner. A developing device having a slope for shifting from the inside of the developer accommodating container to the developer carrying member, wherein an angle θ of the slope with respect to a horizontal plane satisfies the following condition: 20 ° ≦ θ ≦ 80 °; The body has an outer diameter of not more than 15 mm and a surface circumferential speed of 65 mm.
1. An image forming toner for use in an image forming method that rotates at a speed of at least mm / sec. ≦ ψ / φ ≦ 2.8. An image forming toner. 2. The developer bearing member according to claim 1, wherein the peripheral speed of the surface of the developer carrier is 6 or less.
2. A speed of 5 to 260 mm / sec.
4. The toner for forming an image according to claim 1. 3. An electrostatic image carrier is charged, the charged electrostatic image carrier is exposed to form an electrostatic image, and the electrostatic image is developed by developing means having toner to form a toner image. It is formed on a charge image carrier, the formed toner image is transferred onto a transfer material with or without an intermediate transfer member, and the toner image transferred on the transfer material is fixed on the transfer material by a fixing unit. The image forming toner according to claim 1, wherein the toner is used in an image forming method of forming a fixed image by fixing the toner to a toner. 4. A toner having a fluidity index A of 5 to 70%.
The image forming toner according to claim 1, wherein: 5. The toner has at least toner particles and hydrophobic inorganic fine powder, the toner particles contain at least a binder resin, magnetic particles and wax, and the contact angle 水 of the toner with water is as follows. The image forming toner according to claim 1, wherein a condition of 90 ° ≦ 満 足 ≦ 130 ° is satisfied. 6. The image forming toner according to claim 1, wherein a contact angle φ of the slope to water satisfies the following condition: 40 ° ≦ φ ≦ 90 °. 7. An image forming method comprising at least a step of developing an electrostatic image by a developing unit having a toner to form a toner image on an electrostatic image carrier, wherein the developing unit develops the electrostatic image. For toner,
At least a developer accommodating container for accommodating the toner and a developer carrier for carrying and transporting the toner accommodated in the developing container, wherein the developer accommodating container contains the contained toner. A developing device having an inclined surface for moving from the inside of the developer accommodating container to the developer carrier is used. The developer carrier has an outer diameter of 15 mm or less, and a circumferential speed of the surface of 65 mm / sec or more. The angle θ of the slope with respect to the horizontal plane, the contact angle φ of the slope with water, and the contact angle ψ of the toner with water satisfy the following conditions: 20 ° ≦ θ ≦ 80 ° 1.0 ≦ ψ / An image forming method satisfying φ ≦ 2.8. 8. A peripheral speed of the surface of the developer carrier is 6
8. The speed is 5 to 260 mm / sec.
2. The image forming method according to 1., 9. An electrostatic image carrier is charged, the charged electrostatic image carrier is exposed to form an electrostatic image, and the electrostatic image is developed by developing means having toner to form a toner image. It is formed on a charge image carrier, the formed toner image is transferred onto a transfer material with or without an intermediate transfer member, and the toner image transferred on the transfer material is fixed on the transfer material by a fixing unit. 9. The image forming method according to claim 7, wherein the image is fixed to form a fixed image. 10. A toner having a fluidity index A of 5 to 70%.
The image forming method according to claim 7, wherein: 11. The toner has at least toner particles and hydrophobic inorganic fine powder, the toner particles comprising a binder resin,
11. The image forming method according to claim 7, wherein the toner contains at least magnetic particles and a wax, and a contact angle 水 of the toner with water satisfies the following condition: 90 ° ≦ ψ ≦ 130 °. . 12. The image forming method according to claim 7, wherein a contact angle φ of the slope with respect to water satisfies the following condition: 40 ° ≦ φ ≦ 90 °. 13. A process cartridge detachably mounted on a main body of an image forming apparatus, wherein the process cartridge includes an electrostatic image carrier for supporting an electrostatic image and a toner for developing the electrostatic image. Having at least a developing device having a toner for developing an electrostatic image, a developer accommodating container for accommodating the toner, and a toner accommodating in the developing container. At least a developer carrier for transporting, the developer carrier having an outer diameter of 15 mm or less, and rotating at a peripheral speed of 65 mm / sec or more on the surface; The storage container has a slope for transferring the stored toner from the inside of the developer storage container to the developer carrier, the angle θ of the slope with respect to the horizontal plane, and the angle of the slope with respect to water. The contact angle φ and the contact angle of the toner with water ψ
Satisfies the following condition: 20 ° ≦ θ ≦ 80 ° 1.0 ≦ ψ / φ ≦ 2.8. 14. The process cartridge according to claim 13, wherein the peripheral speed of the surface of the developer carrier is 65 to 260 mm / sec. 15. A toner having a fluidity index A of 5 to 70.
15. The process cartridge according to claim 13, wherein the ratio is%. 16. The toner has at least toner particles and hydrophobic inorganic fine powder, the toner particles comprising a binder resin,
16. The process cartridge according to claim 13, wherein the process cartridge contains at least magnetic particles and a wax, and a contact angle 接触 of the toner with water satisfies the following condition: 90 ° ≦ ψ ≦ 130 °. 17. The process cartridge according to claim 13, wherein a contact angle φ of the slope with respect to water satisfies the following condition: 40 ° ≦ φ ≦ 90 °.